Formation of metal–carbon σ-bonds via reactions of alkynes with iridium and their reactivity toward carbon–carbon bond formation with neighboring hydrocarbyl ligands

Abstract

In this account we summarize our recent works on the synthesis of iridium-unsaturated hydrocarbyls that contain metal–carbon σ-bonds and their reactions to produce unsaturated organic compounds regio- and stereospecifically. Iridium–carbon σ-bonds are made during the formation of iridium complexes such as metal-alkynyls, -alkenyls, -carbenes (vinylidenes), -alkyls and carbonyls from reactions of terminal alkynes with iridium. The β-carbon of alkynyl ligand is in general so nucleophilic that it is readily attacked by electrophiles to make the α-carbon of the alkynyl ligand reactive with the nucleophilic carbon of the neighboring hydrocarbyl ligand to form new C–C bonds between hydrocarbyl ligands. These C–C bond forming reactions selectively produce interesting unsaturated organic compounds such as conjugated polyenes, polyene-ynes, cross-conjugated polyenes and cis-olefins. To cite this article: C. S. Chin, H. Lee, C. R. Chimie 8 (2005).